MSc, PhD, DSc, FAPS
Chair in Theoretical Chemistry
- +44 (0)131 451 3083
William Perkin Building
Roles and responsibilities
- Programme Director, Chemistry with Computational Chemistry
- Programme Director, Materials for Sustainable and Renewable Energies
- Director of Studies, Year 3
Theoretical and Computational Chemistry
Research in my group seeks to understand the interplay between geometric structure of molecules and solids, their electronic structure, and physicochemical properties. We are developing new methods and algorithms for finding global minima on potential energy surfaces of molecules and solids. We design new materials with potential applications as energy storage media, new heterogeneous catalysts, and fundamental elements of semiconductor devices. We study elementary chemical processes driven by excess charge.
1. Electron-Driven Proton Transfer
This research has been primarily driven by two factors: (i) damage of DNA by low-energy electrons and (ii) the potential of electron beam lithography to fabricate the next generation of micro- and nano-electromechanical devices. Our theoretical research is performed in collaboration with experimental anion photoelectron and electron energy loss spectroscopy groups. We have recently studied the excess electron mobility along linear molecular chains supported by cyclic hydrogen bonds.
Figure 1.Intermolecular proton transfer triggered by excess electron in the hydrogen-bonded NH3…HCl complex.
2. Electronegativity of Molecular Building Blocks
Can the concept of electronegativity be extended to molecular building blocks? We have determined the electronegativity of ammonium (NH4). Our results confirm the similarity of NH¬4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium, which can cause deviations from the behaviour expected of a conceptual “true alkali metal” with this electronegativity.
Figure 2. The electronegativity and hardness were calculated for the radical of ammonium, NH4.
3. Computational Design of Materials for Hydrogen Storage
Hydrogen storage is one of the most challenging technical barriers in the implementation of hydrogen based energy economy. In collaboration with scientists from the Pacific Northwest National Laboratory we have studied hydrogen storage in materials based on boron and nitrogen. Our studies were focused on the structure and thermodynamics of ammonium borohydride, NH4BH4, and ammonia borane, NH3BH3, materials with extremely high gravimetric and volumetric density of hydrogen. .
Figure 3. The kinetics and thermodynamics of hydrogen release were studied for ammonia borane loaded into a high-surface-area mesoporous silica, SBA-15.
- 'Electron-Driven Acid-Base Chemistry: Proton Transfer from Hydrogen Chloride to Ammonia', S.N. Eustis, D. Radisic, K. H. Bowen, R.A. Bachorz, M. Haranczyk, G.K. Schenter, and M. Gutowski, Science, 319, 936, (2008).
- Is electronegativity a useful descriptor for the “pseudo-alkali-metal” NH4?', A. Whiteside, S.S. Xantheas, M. Gutowski, Chem.Eur. J., 17, 13197 (2011).
- Thermodynamic and Structural Investigations of Ammonium Borohydride a Solid with a Highest Content of Thermodynamically and Kinetically Accessible Hydrogen', A. Karkamkar, S.M. Kathmann, G.K. Schenter, D.J. Heldebrant, N.J. Hess, M. Gutowski, and T. Autrey, Chem. of Mater., 21, 4356, (2009).
- 'Solvation free energies of molecules. The most stable anionic tautomers of uracil', M. Haranczyk, M. Gutowski, A. Warshel, Phys. Chem. Chem. Phys., 10, 4442 (2008).
- Discovery of Most Stable Structures of Neutral and Anionic Phenylalanine through Automated Scanning of Tautomeric and Conformational Spaces', Z. Keolopile, M. Gutowski, M. Haranczyk, J. Chem. Theory Comput., 2013, 9 (10), pp 4374–4381